EP0091055A1 - Procédé de fabrication de poly(éther de phénylène) - Google Patents

Procédé de fabrication de poly(éther de phénylène) Download PDF

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Publication number
EP0091055A1
EP0091055A1 EP83103051A EP83103051A EP0091055A1 EP 0091055 A1 EP0091055 A1 EP 0091055A1 EP 83103051 A EP83103051 A EP 83103051A EP 83103051 A EP83103051 A EP 83103051A EP 0091055 A1 EP0091055 A1 EP 0091055A1
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EP
European Patent Office
Prior art keywords
phenol
weight
phenols
cresol
catalyst
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EP83103051A
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German (de)
English (en)
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EP0091055B1 (fr
Inventor
Juergen Dr. Hambrecht
Herbert Dr. Naarmann
Volker Dr. Muench
Hermann Dr. Brandt
Johann Dr. Swoboda
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols

Definitions

  • the invention relates to a process for producing high molecular weight polyphenylene ethers from monohydric phenols which have alkyl substituents in the two ortho positions or additionally in a meta position, but not in the para position, by oxidative coupling reaction with oxygen at temperatures between 10 and 45 ° C in the presence of a catalyst complex of a copper salt and an organic amine in the presence of an aromatic C 7 -C 10 -hydrocarbon as solvent in the range from 1: 1 to 20: 1 parts by weight, based on the monomeric phenol and optionally an activator.
  • Polyphenylene ethers sometimes referred to as poly (phenylene oxides), are an extremely interesting group of relatively new polymers as a general class of compounds. These polymers, both homo- and copolymers, and methods of making them are disclosed in U.S. Patents 3,306,874, 3,306,875 and 3,432,466. Variations in the process for making these polymers are described in U.S. Patents 3,384,619, 3,639,656, 3,642,699, 3,661,848 and 3,733,299.
  • the polyphenylene ethers obtained are heat-resistant substances and are suitable as blending components for polystyrenes.
  • the most common methods used to prepare polyphenylene ethers include the self-condensation of monohydric phenols by exposure to oxygen in the presence of catalysts.
  • Metal-amine complexes in particular copper-amine complexes, are preferably used as catalysts.
  • Aromatic hydrocarbons are preferably used as solvents.
  • the reaction is usually terminated by removing the catalyst from the reaction mixture. This is done through use aqueous solutions of inorganic or organic acids as described, for example, in DE-OS 21 05 372.
  • Polycarboxylic acids and / or polyaminocarboxylic acids (cf. DE-OS 23 64 319) or other chelating agents such as nitrilotriacetic acid and its sodium salts cf.
  • DE-PS 25 32 477) are also used, the latter also in combination with quaternary ammonium salts (see U.S. Patent 4,026,870).
  • Catalyst separation is also described with the aid of complexing agents from the bisguanide group (cf. DE-OS 24 60 325).
  • the addition of the complex-forming agent also aims to remove the catalyst from the polyphenylene ether as completely as possible, since contamination of the polymer by metal residues leads to a deterioration in the overall property profile of the polymer. In particular, the sensitivity to oxidation and the inherent color are affected.
  • the invention was therefore based on the object of developing a polymerization process which does not have the disadvantages indicated above, or only has it in a weakened form.
  • the di- or tri-substituted phenol contains less than 0.2% by weight, based on the monohydric phenol, of phenol, monosubstituted phenols and polynuclear phenols.
  • the monohydric phenol intended for the polymerization is used with an o-cresol and p-cresol content of in each case less than 0.1% by weight.
  • a monohydric phenol which contains less than 0.05% by weight of o-cresol and less than 0.01% by weight of p-cresol is particularly preferably subjected to the oxidative coupling.
  • a method is particularly preferred in which phenol, m-cresol and polynuclear phenols are present in the starting materials in less than 0.02% by weight.
  • High molecular weight polyphenylene ethers are understood to mean the benzene rings which are substituted by an oxidative coupling of 2,6-dialkylphenols to form a chain of alkyl-substituted, ether-bonded in the para position by oxygen atoms.
  • the polymers have molecular weights of 10,000 to 90,000, preferably 20,000 to 70,000, determined by the method described in "Macromolecular Syntheses" 1 (1978), page 83.
  • High molecular weight polyphenylene ethers have long been known per se from the literature (see, for example, US Pat. No. 3,661,848; US Pat. No. 3,219,625 or US Pat. No. 3,378,505), so that a further description is unnecessary here.
  • the monohydric phenols used to prepare the high molecular weight polyphenylene ethers, which have alkyl substituents in the two ortho positions but not in the para position, are conventional phenols such as 2,6-dimethylphenol, 2,6-diethylphenol, 2-methyl-6 -ethylphenol, 2-methyl-6-propylphenol, 2,6-dibutylphenol, 2,3,6-trimethylphenol and mixtures of these phenols.
  • oxygen is usually introduced into the 10 to 45, preferably 15 to 22 ° C. warm solution of the monomer in the presence of a catalyst complex.
  • the oxygen flow rate is essentially the same as that described in US Pat. Nos. 3,306,874 and 3,306,875.
  • the catalyst complex known for polycondensation is a combination of an amine, e.g. Dibutylamine, diethylamine, picoline, quinoline, pyridine bases, triisopropylamine, dimethylisopropanolamine, triethanolamine, triisopropanolamine or diisopropanolamine with a copper salt, such as copper-I-bromide, copper-I-chloride, copper-I-iodide, copper-II-acetate, copper II-propionate, copper-II-acetoacetic ester or copper-II-acetylacetonate.
  • a copper salt such as copper-I-bromide, copper-I-chloride, copper-I-iodide, copper-II-acetate, copper II-propionate, copper-II-acetoacetic ester or copper-II-acetylacetonate.
  • a preferred range for the amount of the amines used is usually 2.0 to 25.0 mol per 100 mol of the monomer, but the concentration of the amines in the reaction mixture can vary within wide limits, but lower concentrations are expedient.
  • the concentration of the copper salts is kept low and preferably varies from 0.2 to 2.5 moles per 100 moles of the monomer.
  • the proportion of the solvent is usually in the range from 1: 1 to 20: 1, ie at most up to an excess of 20 times the solvent, based on the monomer.
  • an aromatic C 7 to C 10 hydrocarbon should be used as the solvent.
  • Suitable hydrocarbons are, in particular, ethylbenzene, xylene, diethylbenzene or mixtures thereof, ethylbenzene or toluene preferably being used.
  • the solvents are preferably used in the range from 1: 1 to 10: 1 parts by weight, based on the monomeric phenol.
  • reaction mixture can contain an activator such as a diarylguanidine or a diarylformamidine (cf. US Pat. No. 3,544,515).
  • an activator such as a diarylguanidine or a diarylformamidine (cf. US Pat. No. 3,544,515).
  • the polycondensation reaction is preferably carried out at temperatures between 15 and 22 ° C.
  • the oxygen is introduced into the 15 to 22 ° C. warm solution of the monomer in the presence of the amine complex according to the invention.
  • the reaction is complete in a short time, ie the catalyst mixture is metered into the monomer solution in 0.1 to 1.5 hours while gassing with oxygen or air.
  • the reaction solution contains 1 to 30% by weight of polyphenylene ether, 0.005 to 1.5% by weight of metal ions and approximately 0.1 to 6.0% by weight of amine and optionally small amounts of other materials.
  • These reaction solutions are mixed with complexing compounds, e.g. treated the sodium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid or other polyaminocarboxylic acids to separate the metal catalyst contained in the polymer.
  • complexing compounds e.g. treated the sodium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid or other polyaminocarboxylic acids to separate the metal catalyst contained in the polymer.
  • the manner in which the complexing agents are added is not critical.
  • the complex-forming compounds can be added in substance as well as in aqueous solution in the form of their alkali or alkaline earth metal salts.
  • the addition can take place all at once or in several portions, continuously or batchwise, with and without additional water.
  • the separation of the metal component can be done in suitable process devices, e.g. in filter presses, in decantation tanks, peeler centrifuges and the like.
  • the contact time of the complex-forming agent with the catalyst-containing polyphenylene ether phase can vary within wide limits. Reaction times of 1 minute to 5 hours are preferred. Response times of 5 to 30 minutes are often sufficient.
  • the preferred reaction temperature is between 25 and 80 ° C., but temperature ranges below and above can also be used.
  • the metal catalysts can be separated off until they have been completely removed from the polyphenylene ether polymer by repeatedly adding the complex-forming compound and then removing the resulting metal complexes in accordance with the processes already described.
  • an embodiment of the invention is preferred in which the entire amount of catalyst is removed from the polymer in a complexing and separating step.
  • a monohydric phenol preferably 2,6-dimethylphenol
  • 2,6-dimethylphenol which according to the literature (cf. Houben-Weyl-Müller, Methods of Organic Chemistry, Phenols, Part 2, Volume 6/1 C, Georg Thieme Verlag, Stuttgart, 1976, p. 1187 f udzit.Lit.) Described methods of the phenols which interfere with the polymerization, such as phenol, o-cresol, p-cresol, m-cresol and the multinuclear phenols, such as 2,6-dimethyl-1- Hydroxydiphenyl, is separated, used.
  • a preferred aspect of the present process is to facilitate the separation of the catalyst system from the polyphenylene ether solutions.
  • Particular problems arise above all in the case of higher molecular weight polycondensates which are produced from monomers not according to the invention.
  • the presence of polynuclear phenols and p- and o-cresol lead to problems in the phase separation of organic, polyphe- nylene ether-containing solution and aqueous solution containing the complexing agent.
  • Often there is a thick layer of debris at the phase interface which does not dissolve even after standing for several hours and which makes it as impossible as possible to separate the Cu catalyst from the organic phase.
  • Polyphenylene ether solutions which are produced from the monomer mixture according to the invention do not have these disadvantages.
  • the polyphenylene ether can be isolated from the solution by the methods described in the above-mentioned US Pat. Isolation of the polyphenylene ether is not critical to the present invention.
  • the polyphenylene ether by precipitation from a reaction solution using an anti-solvent such as an excess of an alcohol e.g. Methanol.
  • the filtered product can be slurried in alcohol and, if desired, stirred with a decolorizing agent and then the polyphenylene ether is filtered off and converted into films, fibers, molded articles and the like by conventional methods.
  • Other alcohols such as isopropanol, propanol or ethanol can also be used.
  • the amine component of the catalyst can be recovered by distillation or by other conventional methods.
  • a preferred aspect of the present process is the production of polyphenylene ether solutions with a low metal content, from which the polymeric substances can be obtained by so-called total insulation processes, for example by spray drying, steam precipitation and hot water crumbling. This facilitates the economic Use of such processes which are more economical than the known precipitation processes with regard to the required energy, solvent loss and the like.
  • the intrinsic viscosity is determined by measuring 0.5% solutions in chloroform at 30 ° C.
  • a template of 1.3 g of Cu-I bromide and 20 g of 1,4-dimethylpentylamine and 2 g of 2,6-dimethylphenol of the specification given in Table 1 is stirred at 20 ° C for 5 minutes while introducing oxygen and then in Dosed for 30 minutes in a solution of 204 g DMP in 1400 toluene. Then it is ge at 20 ° C for 1 hour stirs. The reaction is carried out in the presence of 30 liters of oxygen per hour.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
EP83103051A 1982-04-07 1983-03-28 Procédé de fabrication de poly(éther de phénylène) Expired EP0091055B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3212925 1982-04-07
DE19823212925 DE3212925A1 (de) 1982-04-07 1982-04-07 Verfahren zur herstellung von polyphenylenethern

Publications (2)

Publication Number Publication Date
EP0091055A1 true EP0091055A1 (fr) 1983-10-12
EP0091055B1 EP0091055B1 (fr) 1986-06-11

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EP83103051A Expired EP0091055B1 (fr) 1982-04-07 1983-03-28 Procédé de fabrication de poly(éther de phénylène)

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EP (1) EP0091055B1 (fr)
DE (2) DE3212925A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337501A (en) * 1964-03-27 1967-08-22 Onderzoekings Inst Res Manganese and cobalt salt-amine complex catalysts in polyphenylene ether formation
EP0047428A1 (fr) * 1980-09-09 1982-03-17 BASF Aktiengesellschaft Procédé pour la préparation d'éthers de polyphénylène

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337501A (en) * 1964-03-27 1967-08-22 Onderzoekings Inst Res Manganese and cobalt salt-amine complex catalysts in polyphenylene ether formation
EP0047428A1 (fr) * 1980-09-09 1982-03-17 BASF Aktiengesellschaft Procédé pour la préparation d'éthers de polyphénylène

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 72, no. 12, 23 March 1970, Columbus, Ohio, US; abstract no. 56083H, page 16; *
CHEMICAL ABSTRACTS, vol. 73, no. 12, 21 September 1970, Columbus, Ohio, US; abstract no. 56496R, LICHOTA D. ET AL: "Poly(phenylene oxides). II. Oxidative polymerization of 2,6-xylenol in the presence of cuprous chloride and triethylenediamine" page 4; *
CHEMICAL ABSTRACTS, vol. 73, no. 2, 13 July 1970, Columbus, Ohio, US; abstract no. 4216E, BAILY J.: "Two-stage oxidative polymerization of 2,6-xylenol to high-molecular-weight poly(phenylene oxide). Synthesis of oligomers. II. Relative activities of phenol, resols, and xylenols" page 2; *
POLIMERY, vol. 14, no. 11, 1969, pages 535 - 538 *
POLIMERY, vol. 15, no. 1, 1970, pages 5 - 7 *

Also Published As

Publication number Publication date
EP0091055B1 (fr) 1986-06-11
DE3364037D1 (en) 1986-07-17
DE3212925A1 (de) 1983-10-13

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